固体燃料化学链燃烧技术的研究进展

化学链燃烧(CLC)能够实现CO2的内分离,同时能提高燃烧效率、减少环境污染。固体燃料储量丰富,研究固体燃料的化学链燃烧将有利于实现固体燃料的高效、经济、清洁利用,具有广阔的应用前景。介绍了固体燃料化学链燃烧的实现途径和技术路线,总结了反应器设计及载氧体的最新研究进展,并指出实现固体燃料化学链燃烧所面临的技术难题。最后,指出高温高压条件下的固体燃料化学链燃烧是未来研究的重要趋势。     

化学链燃烧技术的研究进展

化学链燃烧（Chemical-Looping Combustion 简称CLC)是一种新型的燃烧方式,具有高效、内分离CO2、低NOx 等特点,本文阐述了CLC的基本技术原理,并从氧载体的筛选与制备、化学链燃烧反应器的发展、化学链燃烧系统分析与数值模拟、化学链燃烧与其他技术的耦合、化学链燃烧技术的拓展等方面对当前化学链技术的发展现状和存在不足进行了总结分析,指出了化学发展的5个重点方向。     

固体化学链燃烧技术及污染物释放研究进展

化学链燃烧(CLC)由于其固有的CO_2浓度高、易分离、CO_2减排成本低等优点已成为一种具有发展前景的固体燃料燃烧技术。目前CLC技术由原位气化化学链燃烧(i G-CLC)和氧解耦化学链燃烧(CLOU) 2种技术为代表。采用固体作为燃料燃烧时,其污染元素会以气体形式释放到大气或掺杂到CO_2目标气体中,带来环境及操作问题。论述了固体燃料化学链燃烧的i G-CLC及CLOU2种技术及相关原理,简述了国内外研究现状,并对2种技术的性能和优缺点进行分析。同时,着重对固体燃料化学链燃烧过程中存在的污染元素及其释放规律进行总结。对于固体燃料中的S元素,最终将会大部分转移到气相中并以H2S和SO_2(i G-CLC)或单一SO_2(CLOU)的形式释放,小部分会固存于灰烬中或与氧载体结合。在排放比例方面,随着燃料反应器温度的增加,燃料反应器出口处含硫气体含量上升,同时空气反应器出口处含硫气体含量下降。固体燃料中的N元素将全部转移到气相中并在2种技术中均以N2和NO形式释放,不同之处在于CLOU技术由于氧载体的释氧性使得NO生成偏多,燃料反应器和空气反应器出口处的含氮气体含量与温度的关系与S元素变化一致。固体燃料中Hg元素主要以Hg0和Hg2+分布在气相中,在燃料反应器中主要以Hg0形态存在,而在空气反应器中主要是Hg2+,在CLOU技术中有相当一部分Hg(42.5%)保留在燃烧的灰中。燃料反应器中Hg释放量将随燃料反应器温度的升高而增加,空气反应器的Hg释放量随温度升高而降低。固体燃料化学链燃烧过程中的挥发分作为一种污染物在排放方面也需关注。结果表明燃料类型似乎对燃料反应器出口气体中的焦油量具有决定性影响,目前只发现高挥发分生物质的i G-CLC过程有焦油排放问题,而在CLOU技术中由于燃料反应器中气态氧的存在导致焦油化合物完全燃烧。最后结合污染元素性质及在2种化学链燃烧技术中的释放规律,针对减少相关污染物的排放提出了原料处理及工艺改进建议。     

化学链燃烧技术中载氧体的最新研究进展

介绍了化学链燃烧(CLC)技术的基本概念,指出了其具有在燃烧过程中捕获高浓度CO2,同时消除大气污染物(NOx)等优点.载氧体的性能对其应用非常关键.总结了该领域最近几年新开发的单金属氧化物、复合金属氧化物以及非金属氧化物载氧体的最新研究进展.对具有广泛应用前景的固体燃料化学链燃烧技术及其合适的载氧体做了综述.最后,对化学链燃烧技术中与载氧体相关的重点问题做了展望.     

化学链燃烧技术的研究现状及进展

介绍了化学链燃烧技术的基本概念,总结了现存的载氧剂及其制备方法,指出NiO/NiAl2O4、Fe2O3/Al2O3和CoO-NiO/YSZ是较为理想的金属载氧剂;介绍了4种化学链燃烧反应器模型,指出对能够长期稳定运行的反应器有待进一步研究;概括了化学链燃烧的耦合系统,通过模拟仿真得出其最高系统效率有望达到55.9%;最后,指出化学链燃烧技术可以向固体燃料燃烧、制氢方向发展.     

化学链燃烧在二氧化碳减排中的应用及其研究进展

随着人们对二氧化碳减排的日益重视,化学链燃烧(Chemical Looping Combustion,CLC)技术因为其具有高效、二氧化碳内分离和低NOx等特点,已受到较多关注.介绍了化学链燃烧的基本概念和特点、目前国内外的研究情况以及未来的发展趋势.     

煤化学链制氢技术研究进展

化学链制氢为化石能源的高效清洁利用提供了新思路,是一种新的制氢方式,它具有高效、产品纯度高且分离简单、内分离CO₂、低NO_x等特点,发展前景广阔。本文阐述了化学链制氢的国内外研究现状,基本原理,煤化学链转化过程,介绍了设计的煤化学链制氢工艺实验装置。指出了化学链制氢发展的重点方向：筛选制备性能优异的载氧体、设计优化反应器、固体燃料化学链制氢及其系统开发。     

生物质直接进料的化学链技术进展

化学链技术(chemical-looping technology,CLT)是主要针对化石燃料、生物质等转化过程的清洁高效技术,正在走向商业化。在生物质为原料的CLT中,相较间接进料,直接进料更受关注。本文综述了近年来生物质直接进料的化学链技术研究进展,包括生物质燃烧、气化、制合成气、制氢以及CO_2捕集等。为促进生物质-CLT发展,需克服生物质本身的不利特性,借鉴以煤为原料的CLT开发,并重点研发化学链氧解耦(chemical looping oxygen uncoupling,CLOU)材料。     

化学链制氢技术研究进展

化学链制氢是一种新型的制氢方式,具有高效、产品纯度高且分离简单、内分离 CO₂、低 NO_x等特点,具有广阔的发展前景。阐述了化学链制氢的基本技术原理,并从载氧体的筛选与制备、化学链制氢反应器的发展、化学链制氢原料的选择等方面对当前化学链制氢技术的发展现状和存在不足进行了总结分析,指出了化学链制氢发展的 3个重点方向:筛选制备性能优异的载氧体、设计优化反应器、固体燃料化学链制氢及其系统开发。     

双流化床反应器间气体泄漏规律的数值模拟

建立了描述双流化床化学链燃烧反应器内气固两相流动的数学模型,采用计算流体动力学方法,模拟考察了提升管和鼓泡床相耦合的双流化床内不同单元之间气体泄漏产生原因和影响因素。化学链燃烧系统压力平衡的分析结果表明,反应器间的气体泄漏主要发生在溢流装置和鼓泡床之间;增大溢流装置表观气速,气体泄漏增大,而增大提升管或鼓泡床表观气速时,气体泄漏会随之减小;化学链燃烧系统内颗粒总藏量增加时,气体泄漏会减小;颗粒粒径减小后反应器之间气体泄漏降低。其研究结果对其他循环流化床反应器的设计与工程放大也有一定的借鉴作用。     

基于硫酸钙固体燃料化学链气化过程制备合成气的研究(英文)

Chemical-looping gasification (CLG) is a novel process for syngas generation from solid fuels,sharing the same basic principles as chemical-looping combustion (CLC).It also uses oxygen carriers (mainly metal oxide and calcium sulfate) to transfer heat and oxygen to the fuel.In this paper,the primary investigation into the CLG process with CaSO4 as oxygen carrier was carried out by thermodynamic analysis and experiments in the tube reactor.Sulfur-contained gas emission was mainly H2S rather than SO2 in the CLG process,showing some different features from the CLC.The mass and heat balance of CLG processes were calculated thermodynamically to determinate the auto-thermal operating conditions with different CaSO4/C and steam/C molar ratios.It was found that the CaSO4/C molar ratio should be higher than 0.2 to reach auto-thermal balance.The effect of temperature on the reactions between oxygen carrier and coal was investigated based on Gibbs free energy minimum method and experimental results.It indicated that high temperature favored the CLG process in the fuel reactor and part of syngas was consumed to compensate for auto-thermal system.     

Optimal design of combined cycle power plants with fixed-bed chemical-looping combustion reactors

Process intensification options are explored for near-carbon-neutral, natural-gas-fueled combined cycle (CC) power plants, wherein the conventional combustor is replaced by a series of chemical-looping combustion (CLC) reactors. Dynamic modeling and optimization are deployed to design CLC-CC power plants with optimal configuration and performance. The overall plant efficiency is improved by optimizing the CLC reactor design and operation, and modifying the CC plant configuration and design. The optimal CLC-CC power plant has a time-averaged efficiency of 52.52% and CO₂ capture efficiency of 96%. The main factor that limits CLC-CC power plant efficiency is the reactor temperature, which is constrained by the oxygen carrier material. CLC exhaust gas temperature during heat removal and gas compressor to gas turbine pressure ratio are the most important operating variables and if properly tuned, CLC-CC power plants can reach high thermodynamic efficiencies. © 2018 American Institute of Chemical Engineers AIChE J, 65: e16516 2019     

钠修饰铁矿石载氧体的串行流化床煤化学链燃烧试验

利用1 kW_th串行流化床反应器对钠修饰铁矿石载氧体进行试验研究,考察燃料反应器温度对煤化学链催化燃烧特性的影响。结果表明,钠在820～920℃温度下显著促进了煤气化反应的进行,随着燃料反应器温度的提高,使用Na-铁矿石时燃料反应器出口CO₂浓度明显增大,CO浓度明显降低,在920℃时CO₂捕集效率和碳捕集效率分别达到78.60%和80.54%,而使用纯铁矿石时CO₂捕集效率和碳捕集效率仅为40.27%和45.65%。在高温950℃时Na-铁矿石活性下降,出现烧结和团聚现象,燃料反应器出现滞流态化现象,这可能是钠的化合物熔点较低和载氧体过度还原所导致的。XRD和SEM分析结果显示钠修饰铁矿石促使更多的Fe₂O₃被还原为Fe₃O₄。     

煤/钙基载氧体化学链燃烧操作参数分析

化学链燃烧作为一种新颖的燃烧技术,在化石燃料燃烧释放能量的同时能够有效分离CO2。今以CO2为气化剂气化煤炭,基于Aspen Plus流程模拟软件,研究了煤/钙基载氧体化学链燃烧过程。结果表明,以CO2为煤气化剂,各反应器含水分少,可减少热损失。CaSO4载氧体具有载氧能力大以及反应活性良好等优点。气化炉中CO+H2含量随二氧化碳煤比增大逐渐增加后下降;随温度升高其含量先增加,后趋于平稳。燃料反应器中CO2+H2O含量随载氧体煤比增大,呈现先增大后减小的趋势;随温度升高其含量逐渐下降。空气反应器中CaSO4含量随空载比增大先增加后趋于平稳,随温度升高其含量趋于平稳后下降。气化炉中硫化物和氮化物含量随温度升高而下降,而燃料反应器和空气反应器中硫化物含量随温度升高增加趋势明显,氮化物含量变化不明显。最后确定了关键反应器操作参数:气化炉的二氧化碳煤比为1.8;燃料反应器的载氧体煤比为4.5;空气反应器的空载比为10.5和三反应器的操作温度分别为950、1000和1100℃。     

基于铁基载氧体的煤化学链气化还原过程中氮元素迁移行为

采用热重-质谱-红外联用技术（TG-MS-FTIR），Ar气氛下对煤进行化学链气化实验，实时分析还原过程热解阶段和水蒸气气化反应阶段的过程中固体质量变化和生成气体成分。使用X射线光电子能谱对固相产物进行表面元素分析，探究化学链气化还原过程不同阶段固相产物中氮赋存形态的变化。研究结果表明：载氧体对化学链气化还原过程不同阶段含氮气体释放均有影响。热解阶段载氧体促进自由基的生成，加速了一次热解阶段含氮气体的释放，高温下，载氧体促使NH₃转化为HCN；气化阶段载氧体的加入使半焦的石墨化程度降低，含氮气体释放速率增加。对固相产物中氮的赋存形态而言，载氧体会抑制热解阶段吡咯型氮的分解与转化，高温下，半焦的石墨化和有序化程度降低的同时，镶嵌在煤大分子里面的质子化吡啶裸露出来，质子化吡啶含量降低，吡啶型氮和吡咯型氮的含量大大提升。     

铁基复合载氧体煤化学链气化反应特性及机理

以水蒸气作为气化/流化介质,在流化床中研究了两种铁基复合载氧体的化学链气化反应特性及循环特性,并对气化过程中的反应机理、动力学方程进行了推断。结果表明:温度为920℃时,添加不同修饰物的铁基复合载氧体与煤焦气化的反应活性依次为Fe4Al6K1>Fe4Al6>Fe4Al6Ni1。在多次循环实验过程中,合成气成分保持稳定,表明Fe4Al6K1复合载氧体循环特性良好。XRD谱图分析表明,六次氧化还原实验后的铁基载氧体氧化态仍为Fe₂O₃。K⁺主要以铁酸钾形态存在,该结构有利于促进化学链气化反应。利用高斯函数对气化反应速率进行了峰拟合,拟合结果表明化学链气化主要分为3个阶段:化学链作用阶段、煤气化阶段以及Fe₃O₄向FeO转变的气化阶段。     

CFD simulation of a chemical-looping fuel reactor utilizing solid fuel

A computational fluid dynamic (CFD) study has been carried out for the fuel reactor for a new type of combustion technology called chemical-looping combustion (CLC). CLC involves combustion of fuels by heterogeneous chemical reactions with an oxygen carrier, usually a granular metal oxide, exchanged between two reactors. There have been extensive experimental studies on CLC, however CFD simulations of this concept are quite limited. In the present paper we have developed a CFD model for the fuel reactor of a chemical-looping combustor described in the literature, which utilized a Fe-based carrier (ilmenite) and coal. An Eulerian multiphase continuum model was used to describe both the gas and solid phases, with detailed sub-models to account for fluid–particle and particle–particle interaction forces. Global reaction models of fuel and carrier chemistry were utilized. The transient results obtained from the simulations were compared with detailed experimental time-varying outlet species concentrations (Leion et al., 2008) and provided a reasonable match with the reported experimental data.     

Interaction of mineral matter of coal with oxygen carriers in chemical-looping combustion (CLC)

The chemical-looping combustion (CLC) and chemical-looping with oxygen uncoupling (CLOU) processes are novel solutions for efficient combustion with direct separation of carbon dioxide. These processes use a metal oxide as an oxygen carrier to transfer oxygen from an air to a fuel reactor, where the fuel reacts with the solid oxygen carrier. When utilizing coal in CLC, the oxygen carrier particles could be affected through interaction with the ash-forming mineral matter found in coal, causing deactivation and/or agglomeration. In this work, possible interactions between minerals commonly encountered in coal and several promising oxygen carriers that are currently under investigation for their use in CLC are studied by both experiment and thermodynamic equilibrium calculations. Possible interaction was studied for both highly reducing and oxidizing conditions at 900 °C. Under highly reducing conditions pyrite was found to have by far the most deteriorating effect on the oxygen carrier particles, as the sulfur in the pyrite reacted with the oxygen carrier to form sulfides. Quartz and clay minerals were found to have a rather low influence on the oxygen carriers. Out of the oxygen carriers investigated, CuO/MgAl₂O₄ and the Mn₃O₄/ZrO₂ oxygen carriers tended to be quite reactive towards mineral matter whereas ilmenite has been shown to be the most robust oxygen carrier. Although sulfur can clearly deactivate Ni, Cu and Mn based oxygen carriers under sub-stoichiometric conditions, when the fuel is converted fully to CO₂ and H₂O, sulfides are only expected for Ni-based oxygen carriers.